CN101292379A - Negative electrode for nonaqueous electrolyte secondary battery - Google Patents

Negative electrode for nonaqueous electrolyte secondary battery Download PDF

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Publication number
CN101292379A
CN101292379A CNA2006800388330A CN200680038833A CN101292379A CN 101292379 A CN101292379 A CN 101292379A CN A2006800388330 A CNA2006800388330 A CN A2006800388330A CN 200680038833 A CN200680038833 A CN 200680038833A CN 101292379 A CN101292379 A CN 101292379A
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active material
particle
metal material
layer
secondary battery
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CN101292379B (en
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井手仁彦
安田清隆
百武正浩
松岛英明
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Disclosed is a negative electrode (10) for nonaqueous electrolyte secondary batteries, which comprises an active material layer (12) containing particles (12a) of the active material. A metal material (13) having low lithium compound-forming ability is deposited between particles (12a) by electrolytic plating. The surface of the active material layer (12) is continuously or discontinuously covered with a surface layer (14) which is composed of a metal material similar to or different from the metal material (13) and has an average thickness of not more than 0.25 [mu]m. It is preferable that the surfaces of the particles (12a) are covered with the metal material (13) and air gaps are formed between the particles (12a), which are covered with the metal material (13), within the active material layer (12). The average thickness of the metal material (13) covering the surfaces of particles (12a) is preferably 0.05-2 [mu]m.

Description

Negative electrode for nonaqueous secondary battery
Technical field
The present invention relates to negative electrode for nonaqueous secondary battery and manufacture methods thereof such as lithium secondary battery.
Background technology
The applicant had before proposed following negative electrode for nonaqueous secondary battery, and it possesses: a pair of current collection that contact with electrolyte of surface is with superficial layer with between this superficial layer and dispose and contain the active material layer (with reference to US2005/208379A1, US2006/051675A1, US2006/115735A1) of the particle of the high active material of lithium compound formation ability.The thickness of the superficial layer on this negative pole is 0.3～10 μ m.Owing to have superficial layer on the surface of active material layer, so the particle of active material does not expose on the surface of negative pole.Therefore, even this particle shrinks micronizing, also difficult drop-off because of expanding when discharging and recharging.As a result, if use this negative pole, then has the advantage of the cycle life prolongation of battery.
Described superficial layer has a large amount of fine voids along its thickness direction extension.Fine voids can make the nonaqueous electrolytic solution circulation.Nonaqueous electrolytic solution is compared with aqueous electrolyte, because surface tension is low, so even the size of fine voids is little, this nonaqueous electrolytic solution also can circulate in this fine voids and arrive active material layer., if the thickness of superficial layer is blocked up, then nonaqueous electrolytic solution is difficult to arrive active material layer, the tendency that the overvoltage when having the initial stage to charge increases.As a result, might be when the charging of secondary cell lithium ion generate its dendritic crystal at the surface reduction of superficial layer, or nonaqueous electrolytic solution decomposes, irreversible capacity increases.In addition, also might be anodal impaired.
Summary of the invention
Therefore, the objective of the invention is to, provide a kind of and compare the negative electrode for nonaqueous secondary battery that performance improves more with the negative pole of above-mentioned conventional art.
The invention provides a kind of negative electrode for nonaqueous secondary battery, it is characterized in that: the active material layer that possesses the particle that contains active material, lithium compound forms the low metal material of ability and separates out between this particle by plating, the surface of this active material layer is covered continuously or discontinuously by superficial layer, and described superficial layer is by constituting with the identical or different metal material of this metal material and average thickness is below the 0.25 μ m.
In addition,, the invention provides a kind of manufacture method of negative electrode for nonaqueous secondary battery, it is characterized in that as the preferred manufacture method of described negative pole:
Form by the slurry of the particle that contains active material and to film;
Electroplate this being filmed be immersed under the state that contains in the plating bath that lithium compound forms the low metal material of ability, this metal material is separated out towards opposite side from this side of filming;
Finished to electroplate precipitate into the whole zone of this thickness direction of filming at this metal material before;
Remove this part of not separating out this metal material on filming.
In addition, the invention provides a kind of negative electrode for nonaqueous secondary battery, it is characterized in that: the active material layer that possesses the particle that contains active material, it is that the plating of the plating bath more than 7.1 is separated out between this particle by having used pH that lithium compound forms the low metal material of ability, inside at active material layer, the surface of described particle is covered by described metal material, simultaneously be formed with the space between this particle that is covered by this metal material, the ratio in this space in this active material layer is 15～40 volume %.
Description of drawings
Fig. 1 is the schematic diagram of section structure of an execution mode of expression negative electrode for nonaqueous secondary battery of the present invention.
Fig. 2 is the process chart of the manufacture method of expression negative pole shown in Figure 1.
Fig. 3 is the electron micrograph on the surface of the negative pole that obtains by embodiment 1.
Fig. 4 is the electron micrograph on the surface of the negative pole that obtains by embodiment 2.
Fig. 5 has been to use the primary charging curve of the lithium secondary battery of the negative pole that obtains by embodiment and comparative example.
Embodiment
Below, the present invention will be described based on preferred embodiment and with reference to accompanying drawing.Fig. 1 is the schematic diagram of section structure of an execution mode of expression negative electrode for nonaqueous secondary battery of the present invention.The negative pole 10 of present embodiment possesses collector body 11 and is formed at its active material layer 12 on one side at least.Have again, in Fig. 1, represented only to be formed with the state of active material layer 12, but also active material layer can be formed on the two sides of collector body at the single face of collector body 11.
Active material layer 12 contains the particle 12a of active material.Active material layer 12 for example forms by the slurry that coating contains the particle 12a of active material.As active material, for example can enumerate silicon based material or tin based material, aluminium based material, germanium based material.For improving the capacity density of negative pole Unit Weight, preferred especially silicon based material.As the silicon based material, can use the material that can embed lithium, for example the alloy of elementary silicon, silicon and metal, Si oxide etc.
In active material layer 12, as shown in Figure 1, lithium compound forms the low metal material 13 of ability and is soaked between the particle 12a that is contained in this layer.Metal material 13 is to separate out between particle by plating.In the figure, metal material 13 is represented with the thick line on every side that surrounds particle 12a easily.Metal material 13 preferably is present in the whole zone of the thickness direction of active material layer 12.And the preferred particle 12a that in the metal material 13 of separating out, has active material.Thus one, even this particle 12a shrinks micronizing, also difficult drop-off because of expanding when discharging and recharging.In addition; owing to can guarantee the conductivity of active material layer 12 integral body by metal material 13; therefore can prevent to generate the particle 12a of the isolated active material of electricity effectively, especially can prevent to generate the particle 12a of the isolated active material of electricity effectively in the deep of active material layer 12.This is particularly favourable when the material that uses semiconductor and conductivity deficiency as active material, for example silicon based material.Metal material 13 can be confirmed by the electron microscope mapping that is determination object with this material 13 in the situation of the whole zone infiltration of the thickness direction of active material layer 12.
In the inside of active material layer 12, the metal material 13 that the surface of the particle 12a of active material is separated out covers.Especially, metal material 13 is not the surface that covers this particle 12a in the mode that nonaqueous electrolytic solution can not arrive particle 12a.That is, metal material 13 covers the surface of this particle 12a when guaranteeing that nonaqueous electrolytic solution can arrive the gap of particle 12a.
The average thickness of metal material 13 on surface that is covered with the particle 12a of active material is preferably 0.05～2 μ m, more preferably 0.1～0.25 μ m is thin like this.It is metal material 13 roughly covers the particle 12a of active material continuously with the thickness of minimum surface.Thus, improve energy density, the particle 12a that results from when preventing to discharge and recharge simultaneously shrinks micronized coming off because of expanding.Said herein " average thickness " is based on the value that the metal material 13 actual parts that are covered with are calculated in the surface of particle 12a of active material.Therefore, the part that is not covered by metal material 13 in the surface of the particle 12a of active material is not as the calculating basis of mean value.Have, according to circumstances, the thickness of the metal material 13 on the surface of the particle 12a of covering active material surpasses the thickness of superficial layer 14 described later sometimes again.Its reason is, when making negative pole 10 with method described later, be located in the particle 12a and the lip-deep particle 12a that is positioned at negative pole 10 near the deep (being the collector body 11) of active material layer 12, plating degree difference, the particle 12a that the deep that is positioned at active material layer 12 is arranged, the tendency that is covered thickly by metal material 13.
Between the particle 12a that is covered by metal material 13, be formed with the space.This space has the effect in the space of the stress that the change in volume of the particle 12a of active material when discharging and recharging as mitigation causes.The volume of the particle 12a of the active material that increases because of the charging volume increases part and is absorbed by this space.As a result, the micronizing of this particle 12a is difficult for producing, and can prevent the remarkable distortion of negative pole 10 in addition effectively.In addition, be formed at space between particle 12a and also have effect as the circulation path of nonaqueous electrolytic solution.Considering from above-mentioned viewpoint, the ratio in the space in the active material layer 12, is that voidage is preferably 15～40 volume %, 20～35 volume % more preferably.If be lower than this voidage, then in order to ensure the space of negative pole integral body, need utilize laser processing or punching processing to carry out perforate and handle or utilize etching to carry out perforate and handle, might cause that production cost increases, production stability descends.Voidage can be obtained by the electron microscope mapping.In order to make voidage in above-mentioned scope, for example can suitably select the condition that metal material 13 is separated out by plating between particle 12a.As described condition, current density in the time of can enumerating the composition of plating bath for example or pH, electrolysis etc.
The particle diameter of particle 12a by suitably selecting active material also can be controlled described voidage.From then on viewpoint is considered, the maximum particle diameter of particle 12a is preferably below the 30 μ m, more preferably below the 10 μ m.In addition, if use D 50The particle diameter of value representation particle then is preferably 0.1～8 μ m, 0.3～4 μ m more preferably.The particle diameter of particle can be measured by laser diffraction and scattering formula particle size distribution, electron microscope observation (SEM observation).
If active material is very few with respect to the amount of negative pole integral body, then be difficult to fully improve the energy density of battery, if too much opposite, intensity decreases is arranged then, cause the tendency that active material comes off easily.Consider above-mentioned situation, the amount of active material is preferably 5～80 weight % with respect to negative pole integral body, more preferably 10～70 weight %, more preferably 20～50 weight %.
It is the materials with conductivity that the lithium compound of separating out in active material layer 12 forms the low metal material 13 of ability, as its example, can enumerate the alloy of copper, nickel, iron, cobalt or these metals etc.Even metal material 13 is especially preferred is that the expand overlay film on the surface of shrinking this particle 12a of the particle 12a of active material also is difficult for the high material of ruined ductility.Preferably use copper as such material.So-called " it is low that lithium compound forms ability " is not meant to form intermetallic compound or solid solution with lithium, even or to form lithium also be trace or very unsettled.
In negative electrode for nonaqueous secondary battery in the past, in its active material layer,, contain the particle of conductive materials such as acetylene black or graphite sometimes in order to improve the conductivity of this layer., in the negative pole of present embodiment, preferably in active material layer 12, do not contain the particle of conductive material.Under the situation of the particle that contains conductive material, preferably as much as possible its amount is suppressed at low-level, for example with respect to active material layer 12 preferably below 3 weight %.Its reason will be described in detail in the explanation of the manufacture method of negative pole 10 described later, but according to this reason, be elementary silicon as the most preferred material of active material.
In the negative pole of present embodiment, as previously mentioned, preferred metal materials 13 is present in the whole zone of the thickness direction of active material layer 12.If the rate that exists of the metal material 13 under this state in the active material layer 12 is defined as 100%, do not require in the present invention that then the rate that exists of metal material 13 is 100%.In other words, do not need metal material 13 to be present in the whole zone of the thickness direction of active material layer 12.Present inventors' result of study shows, if the metal material 13 in the active material layer 12 exist rate more than 90%, just can bring into play desirable effect.The rate that exists at metal material 13 is lower than under 90% the situation, can not prevent coming off of particle 12a contained in the active material layer 12 effectively sometimes.The rate that exists of the metal material 13 in the active material layer 12 can be obtained from the microscopic examination of the vertical section of negative pole 10.The rate that exists of for example so-called metal material 13 is 90%, refers to when the vertical section of microscopic examination negative pole 10, and with respect to the thickness of active material layer 12,90% thickness area has metal material 13 to exist.
In the negative pole 10 of present embodiment, also can form thin superficial layer 14 on the surface of active material layer 12.In addition, negative pole 10 also can have such superficial layer.Superficial layer 14 covers active material layer 12 continuously or discontinuously.The average thickness of superficial layer 14 is below the 0.25 μ m, is preferably below the 0.1 μ m, more preferably approaches like this below the 0.08 μ m.For the lower limit indefinite of the thickness of superficial layer 14, also can be 0.The thickness of so-called superficial layer is 0, represents that promptly negative pole 10 does not have superficial layer (active material layer 12 is not covered by superficial layer).Under the situation of the low material of conductivity such as use Si, from guaranteeing the viewpoint of conductivity, the thickness of superficial layer preferably surpasses 0 as active material, and preferred especially average thickness is more than the 0.01 μ m.Said herein " average thickness " is meant that the zone that is not covered by superficial layer 14 in the surface of active material layer 12 is also contained in the interior value of being calculated.Have, the rate that exists of the metal material 13 in above-mentioned active material layer 12 is lower than at 100% o'clock again, and general, active material layer 12 is not covered by superficial layer.
By making negative pole 10 have the superficial layer 14 of described thin thickness or not having this superficial layer, the overvoltage in the time of can reducing the initial stage charging of using negative pole 10 secondary cell for assembling and carrying out this battery.This means and to prevent that lithium is at the surface reduction of negative pole 10 when the charging of secondary cell.The reduction of lithium is relevant with the generation of the dendritic crystal of the reason that becomes the two poles of the earth short circuit.In addition, from the viewpoint consideration that prevents that nonaqueous electrolytic solution from decomposing, it also is favourable can reducing overvoltage.Because if nonaqueous electrolytic solution decomposes, then irreversible capacity increases.In addition, consider that from the not easily vulnerable angle of positive pole it also is favourable can reducing overvoltage.Negative pole 10 has thin superficial layer 14 or does not have this superficial layer, considers it also is favourable from the angle of the capacity density of seeking to improve the secondary cell that possesses this negative pole.
When negative pole 10 had superficial layer 14, this superficial layer 14 covered the surface of active material layer 12 continuously or discontinuously.If the reduced thickness of superficial layer 14, then the covering state of this superficial layer becomes discontinuous state from continuum of states.If the further attenuate of the thickness of superficial layer 14, then as shown in Figure 1, the fine particle 13a that becomes metal material 13 is attached to the state near the surperficial and particle 12a that is positioned at active material layer 12.This fine particle 13a is derived from the plating nuclear (plating nuclei) that produces when metal material 13 is separated out.
When superficial layer 14 covered active material layer 12 surperficial continuously, this superficial layer 14 preferably had a large amount of in its surperficial perforate and the fine voids (not shown) that is communicated with active material layer 12.Fine voids preferably is present in the superficial layer 14 according to the mode that the thickness direction to superficial layer 14 extends.Fine voids is the negotiable space of non-aqueous solution electrolysis liquid.The effect of fine voids is to supply with nonaqueous electrolytic solution in active material layer 12.The amount of fine voids is preferably, when overlooking negative pole 10 surperficial by electron microscope observation, the area ratio that is covered by metal material 13 be coverage rate be below 95%, be preferably below 80% especially, such size below 60% more preferably.
In technology in the past, think the surface that covers active material layer 12 with superficial layer, coming off that the micronizing of active material causes when preventing to discharge and recharge is effective.Although this view is correct, but the present inventors further result of research show, by the existence of the metal material 13 of control in the active material layer 12, though the active material when not using superficial layer also can prevent to discharge and recharge micronizing caused comes off.Specifically distinguish, by covering the surface of the particle 12a that contains in the active material layers 12, and suitable space be set between particle 12a with metal material 13, though when then not using superficial layer can prevent to discharge and recharge yet active material micronizing caused comes off.From then on viewpoint is set out, even its reduced thickness of superficial layer is also enough to required minimum, according to circumstances also superficial layer itself can be set in addition.Superficial layer is not set, from the viewpoint of the dendritic crystal that suppress to produce lithium, and the viewpoint that improves the energy density of battery consider it is favourable.
Superficial layer 14 forms the low metal material of ability by lithium compound and constitutes.This metal material can be identical with the metal material in being present in active material layer 12, also can be different.If consider the easiness of the manufacturing of negative pole 10, the metal material that then preferably is present in the active material layer 12 is identical with the metal material that constitutes superficial layer 14.
As the collector body in the negative pole 10 11, can use with in the past as the used identical collector body of the collector body of nonaqueous electrolyte secondary battery negative electrode.Collector body 11 preferably forms the low metal material of ability by foregoing lithium compound and constitutes.The example of such metal material as previously mentioned.Especially, preferably constitute by copper, nickel, stainless steel etc.In addition, also can use with the copper alloy foil of Corson alloy paper tinsel as representative.The thickness of collector body 11 is not critical in the present embodiment.If consider the strength maintenance of negative pole 10 and the balance that energy density increases, then be preferably 9～35 μ m.
Then, the preferred manufacture method with regard to the negative pole 10 of present embodiment describes with reference to Fig. 2.In this manufacture method, comprise the slurry that uses the particle that contains active material, on collector body 11, form and film, then to this operation of filming and electroplating.
At first, shown in Fig. 2 (a), prepare collector body 11.The slurry that is coated with the particle 12a that contains active material on collector body 11 films 15 with formation then.Slurry also contains binding agent and retarder thinner etc. except that the particle of active material.In addition, slurry can also contain the particle of conductive materials such as a spot of acetylene black or graphite.As binding agent, can use butadiene-styrene rubber (SBR), Kynoar (PVDF), polyethylene (PE), ethylene-propylene-diene terpolymer (EPDM) etc.Can use N-methyl pyrrolidone, cyclohexane etc. as retarder thinner.Preferably the gauge with the particle of the active material in the slurry is decided to be about 14～40 weight %.Preferably the gauge with binding agent is decided to be about 0.4～4 weight %.In them, add retarder thinner to form slurry.
Filming of forming 15 has a large amount of short spaces between particle 12a.To be formed with 15 the collector body 11 of filming is immersed in and contains in the plating bath that lithium compound forms the low metal material of ability.By the dipping in plating bath, plating bath is immersed in film in the described short space in 15, and arrives and film 15 and the interface of collector body 11.Under this state, electroplate (following should the plating method be also referred to as infiltration plating (penetration plating)).Infiltration plating by with collector body 11 as negative electrode, will the two poles of the earth be connected on the power supply carry out as anode electrode is immersed in the plating bath.
In this manufacture method, metal material separated out during importantly the control infiltration was plated.Particularly, this metal material is separated out towards opposite side from 15 the side of filming.Specifically be, shown in Fig. 2 (b)～(d), according to metal material 13 separate out from film 15 and the interface of collector body 11 mode of carrying out towards the surface of filming electroplate.By metal material 13 is separated out in this manner, the enough metal materials 13 of energy successfully cover the surface of the particle 12a of active material, can successfully form the space between the particle 12a that is covered by metal material 13 simultaneously.And easily the voidage in this space is set in the described preferred range.
As the condition of infiltration that metal material 13 is separated out plating, by the forming of plating bath, the pH of plating bath, the current density of electrolysis etc.For example when active material is elementary silicon,, preferably it is adjusted to more than 7.1, more preferably adjust to 7.1～11 about the pH of plating bath.By pH is defined in more than 7.1, being cleaned of surface of the particle 12a of active material forms uniform surface state, can separate out uniformly on the surface of particle 12a, can form the space of appropriateness simultaneously between particle 12a.On the other hand, by pH is defined in below 11, can prevent the significant dissolving of particle 12a.The pH value is to measure under the temperature in when plating infiltration.When using copper, preferably use the cupric pyrophosphate plating bath as this metal material.In addition, when the metal material as the infiltration plating uses nickel, preferably use for example alkaline nickel plating bath.Especially, if use the cupric pyrophosphate plating bath,, also can be easily form described space, so be preferred in the whole zone of the thickness direction of this layer even because when the thickening active material layer.In addition, owing to metal material 13 is separated out on the surface of the particle 12a of active material, and being difficult for producing separating out of metal material 13 between this particle 12a, also is preferred on this aspect of space that can keep between this particle 12a therefore.When using the cupric pyrophosphate plating bath, its plating bath is formed and pH is preferably as follows described.
Cupric pyrophosphate: 85～120g/l
Potassium pyrophosphate: 300～600g/l
Potassium nitrate: 15～65g/l
Bath temperature: 45～60 ℃
Current density: 1～7A/dm 2
PH: adjust to pH7.1～11, preferably adjust to pH 7.1～9.5 by adding ammoniacal liquor and polyphosphoric acids.
Under the situation of the nickel plating bath that uses alkalescence, can use nickelous sulfate 6 hydrates etc. as nickel salt.In order to make plating bath be alkalescence, for example can use ammonium salts such as ammonium chloride as alkali source.Except that these compositions, can also in plating bath, contain boric acid etc.The composition of plating bath and pH are preferably as follows described.
Nickelous sulfate: 100～250g/l
Ammonium chloride: 15～30g/l
Boric acid: 15～45g/l
Bath temperature: 45～60 ℃
Current density: 1～7A/dm 2
PH: the ammoniacal liquor with 25 weight % of the scope of 100～300g/l is adjusted to pH8～11.
If use described each plating bath to permeate plating, precipitating metal material selectively on the surface of the particle of active material then, the surface of this particle is covered by this metal material.If the nickel plating bath and the described cupric pyrophosphate plating bath of alkalescence are compared, the tendency that forms the space of appropriateness in active material layer 12 is then arranged when using the cupric pyrophosphate plating bath, seek the long lifetime of negative pole easily, be preferred therefore.
Contain in filming under the situation of particle of conductive material, have precedence over metal material 13 from filming 15 and the separating out of the interface of collector body 11, metal material 13 is separated out as separating out with the particles of this conductive material easily.As a result, appearance can not make the situation that metal material 13 is successfully separated out according to the mode that forms desirable space between the particle 12a of active material.For anti-phenomenon here, preferably in filming, do not contain the particle of conductive material, even or to contain also be a spot of.
Shown in Fig. 2 (b)～(d), if according to make metal material 13 separate out from film 15 and the interface of collector body 11 mode of carrying out towards the surface of filming electroplate, then in the foremost of evolution reaction portion, the fine particle 13a that is made of the plating nuclear of metal material 13 exists with stratiform by the thickness of constant.Along with the carrying out of separating out of metal material 13, between the adjacent fine particle 13a in conjunction with and form bigger particle, further carry out along with separating out, then between this particle in conjunction with and cover the surface of the particle 12a of active material continuously.
Finished to electroplate precipitate into the whole zone of 15 the thickness direction of filming at metal material 13 before.Thus, shown in Fig. 2 (e), film 15 the surface and near zone become the not state of precipitating metal material 13.Under this state, the region R that clipped by 2 dotted lines among the part of the not precipitating metal material 13 on 15 of filming, for example Fig. 2 (e) (film 15 surface and near zone thereof) is removed.Remove by this, can obtain the negative pole 10 of form shown in Figure 1, promptly be positioned at active material layer 12 the surface and near particle 12a on be formed with the negative pole 10 that adheres to the superficial layer 14 that forms by the fine particle 13a of metal material 13.
About removing of described region R, can use the injection of current for example or carry out wiping etc. with flexibility materials such as sponges.Especially, if use water flow jet, therefore removing of washing after can electroplating simultaneously and region R consider it is preferred from making this aspect of efficient.When carrying out water flow jet, in order to be easy to carry out removing of described region R,, preferably use water miscible as being used to form the binding agent that contains in 15 the slurry of filming.As such binding agent, can enumerate butadiene-styrene rubber (SBR) etc.Have again and since to the internal implementation of active material layer the infiltration plating, so even by described operation water miscible binding agent dissolving is removed, active material itself can not collapse yet.
The surface state of the negative pole 10 that obtains is different because of the degree of removing of described region R.For example under the situation of spraying strong current, removing of region R is more thorough, the fine particle 13a of lip-deep metal material 13 that is scattered in the particle 12a of active material with island is removed fully, forms the thin superficial layer 14 that the continuous film by metal material 13 constitutes on the surface of negative pole 10.On the contrary, under the situation of spraying weak current, removing of region R is so not thorough, the thin superficial layer 14 that exists the discontinuous film by metal material 13 to constitute on the surface of negative pole, or the discontinuous superficial layer 14 that exists the fine particle 13a by the lip-deep metal material 13 of the particle 12a that is scattered in active material with island to constitute.Perhaps, become the state that does not have superficial layer on the surface of negative pole 10.
The negative pole 10 that so obtains is suitable as the negative pole that nonaqueous electrolytic solution secondary battery such as lithium secondary battery is for example used.In such cases, as the positive pole of battery, can be by with positive active material and as required conductive agent and binding agent are suspended in the appropriate solvent, make anode mixture, then it is coated on the collector body, carries out roll-in after the drying and prolong, suppress, cut then, stamping-out obtains.As positive active material, can use known in the past positive active materials such as lithium nickel composite oxide, complex Li-Mn-oxide, lithium cobalt composite oxide.As the barrier film of battery, preferably use synthetic resin system nonwoven fabrics, polyethylene or polypropylene multiple aperture plasma membrane etc.Nonaqueous electrolytic solution constitutes by being dissolved in the solution that forms in the organic solvent as the lithium salts of supporting electrolyte.As lithium salts, for example, but illustration LiClO 4, LiAlCl 4, LiPF 6, LiAsF 6, LiSbF 6, LiSCN, LiCl, LiBr, LiI, LiCF 3SO 3, LiC 4F 9SO 3Deng.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.But scope of the present invention is not subjected to the restriction of these embodiment.
[embodiment 1]
30 seconds of collector body pickling at room temperature that will constitute by the electrolytic copper foil of thick 18 μ m.Handle the back and cleaned for 15 seconds with pure water.The slurry that coating contains the Si particle on collector body is filmed thereby form to reach thickness 15 μ m.The average grain diameter of particle is D 50=2 μ m.Slurry consist of particle: butadiene-styrene rubber (adhesive)=100: 1.7 (weight ratio).The particle that does not contain conductive material in the slurry.
To be formed with the collector body of filming and be immersed in the cupric pyrophosphate plating bath with following plating bath composition, the infiltration plating by electrolysis is carried out copper to filming forms active material layer.The condition regulation of electrolysis is as follows.Use DSE as anode.Use DC power supply as power supply.
Cupric pyrophosphate trihydrate: 105g/l
Potassium pyrophosphate: 450g/l
Potassium nitrate: 30g/l
Bath temperature: 50 ℃
Current density: 3A/dm 2
PH: adjust to pH8.2 by adding ammoniacal liquor and polyphosphoric acids.
Finished the infiltration plating precipitate into the whole zone of the thickness direction of filming at copper before.To have after the collector body of filming of having implemented the infiltration plating picks up from plating bath,, the part of not separating out copper on filming be removed the injection water of filming.Spray to press and be defined as 1MPa.In atmosphere, make its drying then, the negative pole that obtains having structure shown in Figure 1.With electron microscope observation the surface of the negative pole that obtains.Its image as shown in Figure 3.Find out that from this figure the superficial layer that the surface of active material layer is made of copper particle covers continuously.The average thickness of superficial layer is 0.05 μ m.In active material layer, the particle of active material is the resin coated copper covering of 0.18 μ m by average thickness.The result who with copper is the electron microscope mapping of determination object shows that the voidage in the active material layer is 35 volume %.
[embodiment 2]
Except that the injection pressure with current is set at 2MPa, obtained negative pole similarly to Example 1.With electron microscope observation the surface of the negative pole that obtains.Its image as shown in Figure 4.Find out that from this figure the surface of active material layer is covered continuously by the superficial layer by a large amount of copper particle be combined intos.The result of the electron microscope observation of the section of the negative pole that obtains shows that the average thickness of superficial layer is 0.1 μ m, confirms to have formed on this superficial layer the fine voids of extending to its thickness direction.In active material layer, the particle of active material is the resin coated copper covering of 0.18 μ m by average thickness.The result who with copper is the electron microscope mapping of determination object shows that the voidage in the active material layer is 30 volume %.
[embodiment 3]
The filming of water flow jet of utilizing of not carrying out among the embodiment 1 removed.The time of the infiltration plating by adjusting copper is set in 90% with the rate that exists of the copper in the active material layer (metal material 13) in addition.In addition, obtained negative pole similarly to Example 1.With electron microscope observation the surface of the negative pole that obtains, the result does not form the superficial layer of copper on the surface of active material.In addition, in active material layer, the particle of active material is the resin coated copper covering of 0.18 μ m by average thickness.This thickness is to be the value of object mensuration with the position that copper was permeated in the active material layer.With the position that copper was permeated in the active material layer is object, is that the result of the electron microscope mapping of determination object shows that the voidage in this position is 28 volume % with copper.
[embodiment 4]
The filming of water flow jet of utilizing of not carrying out among the embodiment 1 removed, and the time of the infiltration plating by adjusting copper is set in 0.23 μ m with the average thickness of superficial layer in addition.In addition, obtained negative pole similarly to Example 1.With electron microscope observation the surface of the negative pole that obtains, the result confirms to have formed the fine voids of extending to its thickness direction at superficial layer.In addition, in active material layer, the particle of active material is the resin coated copper covering of 0.18 μ m by average thickness.The result who with copper is the electron microscope mapping of determination object shows that the voidage in the active material layer is 28 volume %.
[comparative example 1]
As plating bath, use copper sulfate bath to replace the cupric pyrophosphate plating bath that uses among the embodiment 1.The composition of plating bath is CuSO 4Be 250g/l, H 2SO 4Be 70g/l.Use this plating bath, with 5A/dm 2Current density carried out infiltration plating.Infiltration plating proceeds to copper and separates out in the whole zone of the thickness direction of filming, and forms the superficial layer that is made of copper of thick 3 μ m on filming.In addition, obtained negative pole similarly to Example 1.The result who with copper is the electron microscope mapping of determination object shows that the voidage in this active material layer is 10 volume %.
[estimating 1]
Use has been made lithium secondary battery by the negative pole that embodiment 1～4 and comparative example 1 obtain.Use LiCo as positive pole 1/3Ni 1/3Mn 1/3O 2As electrolyte, use at LiPF with 1mol/L 6Be dissolved in the solution that forms in the mixed solvent of 1: 1 volume % of ethylene carbonate and diethyl carbonate, add the vinylene carbonate of 2 volume % and the electrolyte that obtains.The secondary cell that obtains has been carried out primary charging.Its charging curve as shown in Figure 5.Draw from result shown in Figure 5, compare during with the negative pole that uses comparative example 1, when using the negative pole of embodiment 1～4, the voltage of charging is low, and promptly overvoltage is low.In embodiment 1～4, the overvoltage of embodiment 1 is minimum, increases by the order overvoltage of embodiment 3, embodiment 2, embodiment 4.Have, the overvoltage of negative pole of embodiment 3 that does not form superficial layer is than the high reason of overvoltage of the negative pole of the embodiment 1 that is formed with superficial layer again, and it is as described below that present inventors think.That is,, be the state that exposes on the surface of negative pole so constitute the Si particle of active material layer owing on the negative pole of embodiment 3, do not form superficial layer.Si is the low material of conductivity, can think that the overvoltage of the negative pole that makes embodiment 3 therefrom increases.In contrast, in the negative pole of embodiment 1,, given conductivity to this particle by cover the surface of Si particle thinly with copper.Nor the smooth and easy circulation of obstruction electrolyte.Think that these reasons cause that the negative pole of embodiment 1 compares overvoltage and reduce with the negative pole of embodiment 3.
[estimating 2]
The negative pole that use obtains by embodiment 1～4 and comparative example 1 has been made the lithium secondary battery same with described evaluation 1.20 batteries have been made with regard to each negative pole.A situation arises in short circuit when the secondary cell that obtains has been estimated discharging and recharging of carrying out circulating for 50 times.Its result is as shown in table 1 below.The condition that discharges and recharges is as follows.The speed setting that discharges and recharges is 1C.Charging proceeds to 4.2V with constant current, just remains constant voltage if reach 4.2V, reaches 1/5 o'clock complete charge at current value.Discharge proceeds to 2.7V with constant current, finishes discharge when reaching 2.7V.
Table 1
The incidence of short circuit (%)
Embodiment 1 5
Embodiment 2 15
Embodiment 3 0
Embodiment 4 15
Comparative example 1 55
Draw from the result shown in the table 1, use the secondary cell of the negative pole of each embodiment to compare with the secondary cell of the negative pole that uses comparative example 1, the short circuit incidence is extremely low.Its reason thinks, because the secondary cell of the negative pole of each embodiment when charging, has suppressed the generation of lithium at the reduction of negative terminal surface and the dendritic crystal that causes thereof.
As described in detail above, according to the present invention, even this particle is difficult for also causing that because of the contraction of expanding produces micronizing it comes off when discharging and recharging.And nonaqueous electrolytic solution arrives active material layer easily, so the overvoltage of initial stage charging is reduced.As a result, can prevent to produce the dendritic crystal of lithium on the surface of negative pole.In addition, the decomposition of nonaqueous electrolytic solution is difficult for taking place, thereby can prevent the increase of irreversible capacity.Also subject to damage not of positive pole in addition.

Claims (9)

1. negative electrode for nonaqueous secondary battery, it is characterized in that: the active material layer that possesses the particle that contains active material, lithium compound forms the low metal material of ability and separates out between described particle by plating, the surface of described active material layer is covered continuously or discontinuously by superficial layer, and described superficial layer is by constituting with the identical or different metal material of described metal material and average thickness is below the 0.25 μ m.
2. negative electrode for nonaqueous secondary battery according to claim 1, wherein, the surface of described active material layer is covered discontinuously by the described superficial layer that the particle by described metal material constitutes.
3. negative electrode for nonaqueous secondary battery according to claim 1, wherein, the surface of described active material layer is covered continuously by described superficial layer, is formed with a large amount of fine voids to its thickness direction extension on described superficial layer.
4. negative electrode for nonaqueous secondary battery according to claim 1, wherein, inside at described active material layer, the surface of described particle is covered by described metal material, simultaneously be formed with the space between the described particle that is covered by described metal material, the ratio in the described space in the described active material layer is 15～40 volume %.
5. negative electrode for nonaqueous secondary battery according to claim 4, wherein, the average thickness of described metal material that covers the surface of described particle is 0.05～2 μ m.
6. negative electrode for nonaqueous secondary battery according to claim 1 wherein, does not contain the particle of conductive material in described active material layer, or contains the particle of the following conductive material of 3 weight % of described active material layer.
7. negative electrode for nonaqueous secondary battery, it is characterized in that: the active material layer that possesses the particle that contains active material, it is that the plating of the plating bath more than 7.1 is separated out between described particle by having used pH that lithium compound forms the low metal material of ability, inside at active material layer, the surface of described particle is covered by described metal material, simultaneously be formed with the space between the described particle that is covered by described metal material, the ratio in the described space in the described active material layer is 15～40 volume %.
8. the manufacture method of a negative electrode for nonaqueous secondary battery, it is the manufacture method of the described negative electrode for nonaqueous secondary battery of claim 1, it is characterized in that:
Form by the slurry of the particle that contains active material and to film;
With described film to be immersed under the state that contains in the plating bath that lithium compound forms the low metal material of ability electroplate, described metal material is separated out towards opposite side from a described side of filming;
Finished to electroplate precipitate into the whole zone of described thickness direction of filming at described metal material before;
Remove the part of not separating out described metal material on described the filming.
9. the manufacture method of negative electrode for nonaqueous secondary battery according to claim 8, wherein, described slurry contains binding agent, as described binding agent, uses water misciblely, carries out removing of described part by injection water.
CN2006800388330A 2005-11-08 2006-11-07 Negative electrode for nonaqueous electrolyte secondary battery Expired - Fee Related CN101292379B (en)

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